Abstract
Abstract Photocalorimetry was used to determine the current efficiency of the photoanodic oxidation of halide ions (0.2 M Cl−, Br− and I−) competing with that of water at a polycrystalline TiO2 (rutile) thin film electrode for a range of pH values. For Cl− and Br− the results were checked by chemical analysis (spectrophotometry, polarography) of oxidation products present in the electrolyte solution. Photocurrent efficiencies determined photocalorimetrically and analytically for the formation of halogens (Cl2 and Br2 + Br−3) in acid solution were in satisfactory agreement. Observations made at pH 9 suggest the formation of ClO− and BrO− on the time scale of the experiments. The photocurrent efficiency for oxidation of the halide ions at a given pH was found to increase in the order Cl−, Br−, I− and to decrease, for each species, with increasing pH. This corroborates the trends reported by other workers from rotating ring disk electrode studies using rutile single-crystal electrodes.
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